Illustrated in copending application U.S. Ser. No. 09/838,636, filed concurrently herewith, the disclosure of which is totally incorporated herein by reference, is a toner composition comprised of colorant and an alkali sulfonated polyester-amine resin composition generated from the reaction of an organic diol, an organic diacid, an alkali sulfonated diacid, and an amino-organic diacid.
Illustrated in copending application U.S. Ser. No. 09/838,612, filed concurrently herewith, the disclosures of which is totally incorporated herein by reference, is an ink composition comprised of a vehicle, a colorant and an alkali sulfonated polyester-amine resin generated from the reaction of an organic diol, an organic diacid, an alkali sulfonated diacid, and an amino-organic diacid.
The present invention is generally directed to polymeric resin compositions and processes thereof, and more specifically, to novel sulfonated polyester-amine resins, and which resins can be selected for dry toners, inks such as ink jet inks, and/or colorant, such as pigment dispersants. The aforementioned toners or inks can be selected as marking materials in, for example, a number of xerographic printers, copiers, ink jet printers, fax machines, and the like. In embodiments of the present invention there are provided dry toner compositions comprised of a sulfonated polyester-amine resin, and colorant particles comprised of, for example, carbon black, magnetite, cyan, magenta, yellow, blue, green, or mixtures thereof thereby providing for the development and generation of black and/or colored images; inks that can be selected for ink jet printing, thermal ink jet printing, acoustic ink jet printing and the like, and which ink composition is comprised of a sulfonated polyester-amine resin, a vehicle such as water, glycols mixture thereof and the like, and a colorant such as a dye or pigment, thereby providing, for example, developed images with excellent waterfastness and low smear print quality colorant; a pigment dispersant comprised of a sulfonated polyester-amine resin, and which dispersion is utilized in inks formulations or toner compositions, especially compositions prepared by chemical processes, such as emulsion aggregation process and the like, thereby providing an excellent colorant dispersion and high projection efficiency; and a sulfonated polyester-amine resin of, for example, the following formula, and processes for the preparation thereof by, for example, melt condensation 
wherein M is a suitable metal, such as an alkali such as sodium, potassium, or lithium, or a hydrogen atom; Y is an alkylene inclusive of alkyleneoxyalkylenes, each with, for example, from about 2 to about 25 carbon atoms, such as ethylene, propylene, 1,2-propylene, propylene oxy propylene, or 1,2-butylene; X is an arylene with, for example, from about 7 to about 30 carbon atoms, such as 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, or an alkylene; and m, n and o each represent the number of random segments wherein random refers, for example, to the segments m, n and o that do not follow an algorithmic pattern, that is these segments usually follow no pattern as opposed to alternating or block.
The sulfonated polyester-amine resin can be selected as a colorant dispersant, and for toners and inks, which can be employed in known electrophotographic imaging, digital, printing processes, including color processes, ink jet, and lithography. Toners comprised of the aforementioned sulfonated polyester amine are especially useful for the development of colored images with excellent line and solid resolution, and wherein substantially no background deposits are present, and wherein excellent toner electrical stability is retained after multiple printing such as from about 500,000 to 1,000,000 print cycles. Additionally, inks comprised of the sulfonated polyester-amine possess excellent print quality attributes, such as low smear of, for example, less than about a 0.2 change in optical density values after smearing, and excellent waterfastness such as about 90 to about 95 percent on plain papers. Moreover, when the aforementioned resins are utilized as a colorant like pigment dispersant, the dispersant can be selected to prepare chemical toners, such as for example emulsion aggregation toners as disclosed in U.S. Pat. No. 5,593,807, the disclosure of which is totally incorporated herein by reference, and wherein the colorants stabilized by the sulfonated polyester amine provide excellent colorant dispersants of small particle diameter size of between about 20 to about 300 nanometers, and more specifically, between about 50 to about 150 nanometers, thus resulting in high image projection efficiencies, especially on transparency media, such as from about 90 to about 100 percent as measured by the Match Scan II by Milton-Roy.
In embodiments of the present invention, the sulfonated polyester amine resin can be utilized for the preparation of aqueous based pigment dispersions, that is, pigments or colorants dispersed in an aqueous environment and stabilized with a resin, such as the sulfonated polyester amine resin of the present invention, which dispersion is stable and does not usually settle out or aggregate during storage, and wherein the stable dispersion can be utilized for the preparation of chemical toners or inks. Advantages associated with colorant dispersions are that excellent and substantially complete dispersion within the toners are obtained, thus leading to developed images of high projection efficiency, and wherein the transparency projection efficiency obtained is, for example, from about 90 to about 100 percent as measured by the Match Scan II spectrophotometer from Milton-Roy.
In yet another embodiment of the present invention, the sulfonated polyester-amine resins can be selected for inks utilized in ink jet piezoelectric printers. One of the continuing shortfalls in current ink jet products is excellent waterfastness and low smear. For dyes in particular, this has largely been overcome through the introduction of waterfastness agents, such as polyelectrolytes, for example Calgon and related poly(diallyldiethylammonium) bromide materials. In the present invention, the use of amine containing sulfonated polyester resins readily form ammonium-sulfate ionic salts by pH adjustment. These water dispersible polymeric cationic salt complexes fix or attach to plain papers and enable excellent waterfastness and low smear properties.
The sulfonated polyester-amine resins can, as indicated hereinbefore, be utilized for the preparation of toners, and more specifically, toners generated by emulsion aggregation process such as illustrated in U.S. Pat. Nos. 5,593,807; 5,840,462, and 5,853,944, the disclosures of which are totally incorporated by reference. More specifically, in embodiments, the polyester resins are useful in the preparation of small average toner particle sizes of, for example, from about 3 microns to about 9 microns, and about 5 microns in volume average diameter without resorting to classification processes, and wherein narrow geometric size distributions are attained, such as from about 1.16 to about 1.30, and more specifically, from about 1.18 to about 1.25. High toner yields also result, such as from about 90 percent to about 98 percent in embodiments of the present invention.
Illustrated in the above mentioned U.S. Pat. No. 5,593,807, the disclosure of which is totally incorporated herein by reference in its entirety, is a process for the preparation of toner compositions comprising, for example,
(i) preparing an emulsion latex comprised of sodio sulfonated polyester resin particles of from about 5 to about 500 nanometers in size diameter by heating said resin in water at a temperature of from about 65xc2x0 C. to about 90xc2x0 C.;
(ii) preparing a pigment dispersion in water by dispersing in water from about 10 to about 25 weight percent of sodio sulfonated polyester and from about 1 to about 5 weight percent of pigment;
(iii) adding the pigment dispersion to the latex mixture with shearing, followed by the addition of an alkali halide in water until aggregation results, for example, by an increase in the latex viscosity of from about 2 centipoise to about 100 centipoise;
(iv) heating the resulting mixture at a temperature of from about 45xc2x0 C. to about 55xc2x0 C. thereby causing further aggregation and enabling coalescence, resulting in toner particles of from about 4 to about 9 microns in volume average diameter and with a geometric distribution of less than about 1.3; and optionally
(v) cooling the product mixture to about 25xc2x0 C. and followed by washing and drying. The toners of this patent may possess disadvantages in that, for example, the use of such toners in high speed printers results in a decrease in the developer stability and developer lifetimes due primarily to triboelectric charge loss, especially after multiple print cycles of about 100,000 to about 300,000. These and other disadvantages and problems are minimized, or avoided with the sulfonated polyester amine toner resins of the present invention, and wherein the developer life is extended beyond 500,000 print cycles, and more specifically, up to about 1,000,000 print cycles.
Numerous processes are known for the preparation of toners, such as, for example, conventional toner polyester processes wherein a resin is melt kneaded or extruded with a pigment, micronized and pulverized to provide toner particles with a volume average particle diameter of from about 9 microns to about 20 microns, and with a broad geometric size distribution of from about 1.26 to about 1.5. In these processes, it is usually necessary to subject the aforementioned toners to a classification procedure such that a toner geometric size distribution of from about 1.2 to about 1.4 is attained. Also, in the aforementioned conventional process, low toner yields after classifications may be obtained. Generally, during the preparation of toners with average particle size diameters of from about 11 microns to about 15 microns, toner yields range from about 70 percent to about 85 percent after classification. Additionally, during the preparation of smaller sized toners with particle sizes of from about 7 microns to about 10 microns, lower toner yields may be obtained after classification, such as from about 50 percent to about 70 percent. In some instances, when the aforementioned toners are utilized in high speed reprographic engines, wherein multiple prints are provided, the developer is constantly refreshed with toner, and after prolonged usage, such as from about 100,000 to about 300,000 copy or print cycles, the image quality may be deficient due to triboelectrical charge loss of the developer. There is thus a need for toner compositions minimized or avoided whereby the resin component has a built-in charge such that tribo loss is in a developer, especially after about 300,000 print cycles, and up to about 1,000,000 print cycles. In the present invention, this deficiency is overcome by the utilization of a charged toner resin, such as a sulfonated polyester amine, and wherein the amine moiety and sodiosulfonated moiety provide stable triboelectric charge to the developer utilized in, for example, a reprographic machine.
In U.S. Pat. No. 5,290,654, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of toners comprised of dispersing a polymer solution comprised of an organic solvent and a polyester, and homogenizing and heating the mixture to remove the solvent and thereby form toner composites.
Emulsion/aggregation/coalescing processes for the preparation of toners are illustrated in a number of Xerox patents, the disclosures of which are totally incorporated herein by reference, such as U.S. Pat. Nos. 5,290,654, 5,278,020, 5,308,734, 5,370,963, 5,344,738, 5,403,693, 5,418,108, 5,364,729, and 5,346,797; and also of interest may be U.S. Pat. Nos. 5,348,832; 5,405,728; 5,366,841; 5,496,676; 5,527,658; 5,585,215; 5,650,255; 5,650,256 and 5,501,935. The appropriate components and processes of these Xerox Corporation patents may be selected for the present invention in embodiments thereof.
It is a feature of the present invention to provide a resin composition and processes thereof with many of the advantages illustrated herein.
It is another feature of the present invention to provide a sulfonated polyester-amine resin composition and processes thereof with many of the advantages illustrated herein.
In another feature of the present invention there is provided a melt condensation process for the preparation of a sulfonated polyester-amine resin.
Further, in a feature of the present invention there is provided a melt condensation process for the preparation of a sulfonated polyester-amine resin derived from an organic diol and mixture of organic diacid.
In an added feature of the present invention, there is provided a melt condensation process for the generation of a sulfonated polyester-amine resin, wherein the organic diol selected is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, mixtures thereof and the like, and which diol is selected in an amount of, for example, from about 0.45 to about 0.55 mole percent of the sulfonated polyester-amine resin.
In yet another feature of the present invention there is provided a melt condensation process for the preparation of a sulfonated polyester-amine resin, wherein the organic diacid mixture selected is comprised of from about 80 to about 95 parts or percent of organic diacid, such as terephthalic acid of from about 1 to about 10 parts or percent of a sodiosulfonated organic diacid such as sodio 5-sulfoisophthalic acid, and from about 0.5 to about 15 parts or percent of amine containing organic diacid such as aspartic acid.
Moreover, in a feature of the present invention there are provided sulfonated polyester-amine resins selected for the preparation of black and colored toner compositions.
Another feature of the present invention resides in the provision of a sulfonated polyester-amine resin for the generation of black and colored ink compositions.
In yet another feature of the present invention there are provided sulfonated polyester-amine resins for the generation of a heat and cold resistant, long shelf life, such as from about 30 to about 360 days, of stable black and colored dye or pigmented aqueous dispersions.
Also, in another feature of the present invention there are provided simple and economical in situ processes for the generation of black and colored dry toner compositions by an emulsion aggregation process, and wherein a sulfonated polyester-amine is selected as the resin, and wherein the resulting toner displays a volume average diameter of, for example, from between about 1 to about 20 microns, and more specifically, from about 1 to about 7 microns in volume average diameter, and with a narrow GSD of, for example, from about 1.15 to about 1.35, and more specifically, from about 1.14 to about 1.22 as measured by a Coulter Counter.
In a further feature of the present invention there is provided a process for the preparation of sulfonated polyester-amine containing toner compositions by melt mixing, kneading or extrusion processes, and which toner possesses a volume average diameter of from between about 1 to about 20 microns, and preferably from about 1 to about 7 microns in volume average diameter, and with a narrow GSD of, for example, from about 1.25 to about 1.35 as measured by a Coulter Counter.
Additionally, in a further feature of the present invention there is provided a sulfonated polyester-amine based toner for high speed reprographic printing apparatus with excellent developer life, such as from about 500,000 to about 1,000,000 cycles, without or with minimum development loss associated with charge in stability.
Also, in a further feature of the present invention there is provided a process for the preparation of ink compositions containing a sulfonated polyester-amine.
In yet a further feature of the present invention there is provided a process for the preparation of ink compositions with a sulfonated polyester-amine, and which inks permit excellent waterfastness and low smear print quality.
Moreover, in a further feature of the present invention there is provided an economical process for the preparation of aqueous colorant dispersions comprised of a sulfonated polyester-amine and a dye or pigment, and wherein the colorant dispersion emulsion can be aggregated and coalesced with complexing agents like diamines, trialkyl amines, divalent metal salts, polyelectrolytes, dendrimers, iron complexes, cobalt complexes, and the like.
In another feature of the present invention there is provided a composite toner of polymeric resin with colorant, and a sulfonated polyester-amine pigment dispersion, which toner enables a high projection efficiency, such as from about 950 to about 99 percent as measured by the Match Scan II spectrophotometer available from Milton-Roy.
These and other features of the present invention are accomplished in embodiments by the provision of a sulfonated polyester-amine resins and process thereof.
Aspects of the present inventionxe2x80x94Jean to copy the final claims here; a sulfonated polyester-amine resin contained in a toner or ink composition, and which resin is generated by the melt condensation reaction of an organic diol and a mixture of organic diacids comprised of from about 80 to about 95 parts percent of organic diacid, such as terephthalic acid, from about 1 to about 10 parts percent of a sodiosulfonated organic diacid, such as sodio 5-sulfoisophthalic acid, and from about 0.5 to about 15 parts percent of amine containing organic diacid, such as aspartic acid, and wherein the total amount of diacids is about 100 part percent; sulfonated amine polyester resins which contain sulfonated groups thereby rendering them dissipatible, that is, they form spontaneous emulsions in water without the use of organic solvents, especially above the glass transition temperature, Tg, of the polyester resin, and which resin also contains a number of amine moieties, thereby enabling excellent toner stable triboelectric performance, the ability to form cationic complexes with the sulfate moiety and thus permitting the ink jet print quality performance improvements; and a sulfonated polyester-amine resin obtained by a melt condensation process comprised of charging a reactor equipped with a mechanical stirrer and distillation apparatus with from about 95 to about 105 mole percent of a glycol, such as propylene glycol, diethylene glycol, dipropylene glycol or mixtures thereof, with from about 35 to about 40 mole percent of an organic diacid, such as terephthalic acid, from about 5 to about 15 mole percent of a sulfonated organic diacid, such as sodio 5-sulfoisophthalic acid or dimethyl 5-sulfo-isophthalate sodium salt, and from about 0.5 to about 15 mole percent of amine containing organic diacid, such as aspartic acid, and wherein the total organic diacid amount is from about 48 to about 52 mole percent, and a polycondensation catalyst, such as stannic acid or tetrabutyl titanate, selected in an amount of from about 0.005 to about 0.5 mole percent. The reactor contents are then heated to a temperature of from about 150xc2x0 C. to about 190xc2x0 C., and wherein water or alcohol is distilled off during a period of from about 3 to about 6 hours. Thereafter, the temperature is increased to from about 205xc2x0 C. to about 220xc2x0 C., and the pressure is reduced from atmospheric pressure to about 1 mm-Hg over a duration of, for example, from about 3 to about 6 hours, during which water or alcohol and the excess glycol are distilled off. The pressure of the reaction is then reverted back to atmospheric pressure and the contents discharged through a bottom drain of the reactor to provide a sodiosulfonated polyester-amine resin, such as a random copoly(1,2-propylene-terephthalate)-copoly(1,2-propylene-sodio 5-sulfo-isophthalate)-copoly(1,2-propylene-aspartate), with a glass transition temperature of, for example, from about 50xc2x0 C. to about 65xc2x0 C., a number average molecular weight of from about 2,000 to about 50,000 grams per mole, a weight average molecular weight of from about 5,000 to about 100,000 grams per mole, and a polydispersity of, for example, from about 2 to about 30.
Examples of sulfonated polyester-amines generated with the processes of the present invention include, but are not limited to, copoly(1,2-propylene-terephthalate)-copoly(1,2-propylene-sodio 5-sulfoisophthalate)-copoly(1,2-propylene-aspartate), copoly(neopentylene-terephthalate)-copoly(neopentylene-sodio 5-sulfoisophthalate)-copoly(neopentylene-aspartate), copoly(1,2-propylene-ethyleneoxyethylene-terephthalate)-copoly(1,2-propylene-ethyleneoxyethylene-sodio 5-sulfoisophthalate)-copoly(1,2-propylene-ethyleneoxyethylene-aspartate), copoly(1,2-propylene-terephthalate)-copoly(1,2-propylene-potasio 5-sulfoisophthalate)-copoly(1,2-propylene-aspartate), copoly(neopentylene-terephthalate)-copoly(neopentylene-potasio 5-sulfoisophthalate)-copoly(neopentylene-aspartate), and copoly(1,2-propylene-ethyleneoxyethylene-terephthalate)-copoly(1,2-propylene-ethyleneoxy ethylene-potasio 5-sulfoisophthalate)-copoly(1,2-propylene-ethyleneoxyethylene-aspartate).
Examples of organic diols utilized in preparing the aforementioned polyesters of the present invention include diols or glycols, such as alkylene glycols with a carbon chain length of, for example, from about 1 to about 25 carbon atoms, and more specifically, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol, 1,4-pentylene glycol, 1,5-pentylene glycol, hexylene glycol, heptalyne glycol, diethylene glycol, dipropylene glycol, cyclohexane diol, 2,2-dimethyl propane diol, neopentylene glycol, octylene glycol, cyclohexane dimethanol, mixtures thereof, and the like; and which glycols are employed in various effective amounts of, for example, from about 45 to 55 mole percent of the resin product.
Various organic diacids or esters of diacids can be selected to form the amine resin products of the present invention, such as those selected from the group consisting of fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, adipic acid, succinic acid, suberic acid, 2-ethyl succinic acid, glutaric acid, dodecylsuccinic acid, 2-methyladipic acid, pimelic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2-cyclohexanedioic acid, 1,3-cyclohexanedioic acid, 1,4-cyclohexanedioic acid, dialkyl esters wherein alkyl contains from about 2 to about 22 carbon atoms, and are esters of malonate, succinate, fumarate, itaconate, terephthalate, isophthalate, phthalate, cyclohexanedioate, and mixtures thereof, and which diacids are optionally selected in an amount of from 35 mole percent to about 0.45 mole percent based on about 100 mole percent of resin product.
Examples of sulfonated organic diacids or esters of diacids include those selected from the group comprised of sodio 5-sulfoisophthalic acid, potasio 5-sulfoisophthalic acid, sodio 2-sulfoterephthalic acid, potasio 2-sulfoterephthalic acid, dimethyl 5-sulfoisophthalate sodium salt, dimethyl 5-sulfoisophthalate potassium salt, and mixtures thereof, and which diacids are optionally selected in an amount of from 1 mole percent to about 10 mole percent, based on about 100 mole percent of resin product.
Amine containing organic diacid or esters of diacids selected for the resin processes illustrated herein include, for example, aspartic acid, dimethyl aspartate, diethyl aspartate, dipropyl aspartate and the like, and which diacids are optionally selected in an amount of from 1 mole percent to about 10 mole percent, based on about 100 mole percent of the resin product.
The transesterification or polycondensation catalyst utilized for the preparation of the invention polyester amine, and which catalyst is an optional component, is selected, for example, from the group consisting of tetraalkyl titanates, dialkyltin oxide, such as dibutyltin oxide hydroxide or stannic acid available as FASCAT 4100 from Elf Atochem, aluminum alkoxide, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, or mixtures thereof and the like, and which catalyst can be selected in an amount of, for example, from about 0.001 mole percent to about 0.01 mole percent, based on about 100 mole percent of resin product.
In some instances, colorants, such as pigments available in the wet cake form or concentrated form containing water, can be easily dispersed in the polyester sulfonate amine resin product illustrated herein utilizing a homogenizer or stirring to form the dispersion; or there can be selected colorants which are available in a dry form to permit a dispersion in water effected by microfluidizing using, for example, an M-110 microfluidizer and passing the colorant or colorant dispersion from about 1 to about 10 times through the chamber of the microfluidizer, or by sonication, such as using a Branson 700 sonicator, with from about 1 to about 10 weight percent of the sodiosulfonated polyester-amine resin. The resulting colorant dispersion can be utilized to generate toners by an emulsion aggregation process, such as the processes, for example, disclosed in U.S. Pat. No. 5,840,462, the disclosure of which is totally incorporated herein by reference.
Various known colorants or pigments present in the toner in an effective amount of, for example, from about 1 to about 25 percent by weight of the toner, and more specifically, in an amount of from about 1 to about 15 weight percent, that can be selected include carbon black like REGAL 330(copyright); and other known suitable carbon blacks; magnetites, such as Mobay magnetites MO8029(trademark), MO8060(trademark); Columbian magnetites; MAPICO BLACKS(trademark) and surface treated magnetites; Pfizer magnetites CB4799(trademark), CB5300(trademark), CB5600(trademark), MCX6369(trademark); Bayer magnetites, BAYFERROX 8600(trademark), 8610(trademark); Northern Pigments magnetites, NP-604(trademark), NP-608(trademark); Magnox magnetites TMB-100(trademark), or TMB-104(trademark); and the like. As colored pigments, there can be selected cyan, magenta, yellow, red, green, brown, blue or mixtures thereof. Specific examples of pigments include phthalocyanine HELIOGEN BLUE L6900(trademark), D6840(trademark), D7080(trademark), D7020(trademark), PYLAM OIL BLUE(trademark), PYLAM OIL YELLOW(trademark), PIGMENT BLUE 1(trademark) available from Paul Uhlich and Company, Inc., PIGMENT VIOLET 1(trademark), PIGMENT RED 48(trademark), LEMON CHROME YELLOW DCC 1026(trademark), E.D. TOLUIDINE RED(trademark) and BON RED C(trademark) available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL(trademark), HOSTAPERM PINK E(trademark) from Hoechst, and CINQUASIA MAGENTA(trademark) available from E.I. DuPont de Nemours and Company, and the like. Generally, colorants that can be selected are cyan, magenta, or yellows, and mixtures thereof. Examples of magentas are 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like. Illustrative examples of cyans include copper tetra(octadecyl sulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed in the Color Index as CI 74160, CI Pigment Blue, and Anthrathrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like; while illustrative examples of yellows that may be selected are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4xe2x80x2-chloro-2,5-dimethoxy acetoacetanilide, and Permanent Yellow FGL. Colored magnetites, such as mixtures of MAPICO BLACK(trademark), and cyan components may also be selected as colorants. These colorants selected are present in various effective amounts as indicated herein, and generally from about 1 weight percent to about 65 weight, and more specifically, from about 2 to about 12 percent of the toner. Many, and in embodiments all, of the aforementioned pigments can be selected for the formulation of inks.
Colorants include dyes such as known dyes like food dyes, pigments, mixtures thereof, mixtures of pigments, mixtures of dyes, and the like.
Surface additives that can be added to the dry toner composition after isolation by, for example, filtration, and then optionally followed by washing and drying include, for example, metal salts, metal salts of fatty acids, metal oxides, colloidal silicas, titanium oxides, mixtures thereof, and the like, which additives are each usually present in an amount of from about 0.1 to about 2 weight percent, reference U.S. Pat. Nos. 3,590,000; 3,720,617; 3,655,374 and 3,983,045, the disclosures of which are totally incorporated herein by reference. Specific additives include zinc stearate, silicas, such as AEROSIL R972(copyright), and other silicas available from Cabot Corporation or Degussa Company. These additives can each be selected in amounts of, for example, from about 0.1 to about 2 percent, and which additives can be incorporated during aggregation, or blended into the formed toner product. The toner may also include known charge additives in effective amounts of, for example, from about 0.1 to about 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, the disclosures of each of these patents being totally incorporated herein by reference, negative charge enhancing additives like aluminum complexes, and the like. Other known positive and negative enhancing charge additives may also be selected.
Developer compositions can be prepared by mixing the toners obtained with the processes of the present invention with known carrier particles, for example from about 2 percent toner concentration to about 8 percent toner concentration, including coated carriers, such as steel, ferrites, and the like, reference U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference. The carrier particles may also be comprised of a carrier core with a polymer coating, or coatings thereover, and dispersed therein a conductive component like a conductive carbon black in an amount, for example, of from about 5 to about 60 weight percent.
Imaging methods are also envisioned with the toners of the present invention, reference for example a number of the patents mentioned herein, and U.S. Pat. Nos. 4,265,660; 4,585,884; 4,563,408 and 4,584,253, the disclosures of which are totally incorporated herein by reference.
The present invention in embodiments is also directed to ink compositions and processes thereof, and wherein the disclosed sulfonated polyester-amine resins are selected, and wherein the inks and developed images thereof possess excellent waterfastness of, for example, from about 95 to about 99 percent, as measured by water soaking prints, and evaluating changes in optical density; high lightfastness values wherein, for example, extended exposure of developed prints in light box exposed to Xenon lamp evidence no or minimal change in optical density or color change as measured with a color densitometer; low smear values of, for example, between about 0.01 to about 0.25, and more specifically, about 0.01 to about 0.15 as measured using a wet smear fixture capable of providing a constant pressure across a printed page; low product cost where the final cost of the resin and pigment is substantially less costly (about 10 to about 40 percent) than a number of commercially available products; high image ink resolution from printheads capable of delivering 1200xc3x971200 dpi resolution or higher; excellent print quality in terms of high optical densities of between about 1.4 to about 1.7 for black and between about 0.7 to about 1.3 for color; minimal ink line edge raggedness of between about 0.1 to about 6, and low ink intercolor bleed values of between about 5 to about 20, and more specifically, between about 5 to about 15 on a variety of substrates as measured using an HR camera; excellent ink jetting capability with high drop velocity; excellent latency of between about 50 to about 500 seconds for first drop; larger ink drop mass or drop volume which provides optimal optical density in a single pass; high frequency of between about 12 to about 24 KHz, and more specifically, between about 15 to about 24 KHz response which allows for high speed printing; excellent ink printhead recoverability and maintainability; excellent ink stability; minimal ink and colorant settling; a substantial lack of printhead kogation, and wherein the inks when selected for ink jet processes enables the minimization of paper curl, and wherein smearing is avoided or minimized.
The inks can be comprised of a vehicle, a colorant, a sulfonated polyester-amine resin and optionally humectants, surfactants and other known or to be developed ink additives.
Liquid ink vehicle examples include water, a mixture of water and a miscible organic component, such as glycols like ethylene glycol, propylene glycol, diethylene glycols, glycerine, dipropylene glycols, polyethylene glycols, polypropylene glycols; amides, ethers, carboxylic acids, esters, alcohols, organosulfides, organosulfoxides, sulfones, dimethylsulfoxide, sulfolane, alcohol derivatives, carbitol, butyl carbitol, cellusolve, ether derivatives, amino alcohols, ketones, 2-pyrrolidinone, other water miscible components, and mixtures thereof. When mixtures of water and water miscible organic liquids are selected as the liquid vehicle, the water to organic ratio may be in any effective range, and can, for example, be from about 100:0 to about 30:70, and more specifically, from about 97:3 to about 50:50, although the ratio may be outside these ranges. The nonwater component of the liquid vehicle generally serves as a humectant and which component possesses, for example, a boiling point higher than that of water, about 100xc2x0 C. The colorant or pigment dispersion can be mixed with different humectants or solvents for generating ink jet inks including ethyleneglycol, diethyleneglycol, propyleneglycol, dipropylene glycol, polyethyleneglycols, polypropylene glycols, glycerine, trimethylolpropane, 1,5 pentanediols, 1,6 hexanediols, diols and triols containing about 2 to about 10 carbons; sulfoxides, for example dimethylsulfoxide, alkylphenyl sulfoxides; sulfones, for example sulfolane, dialkyl sulfones, alkyl phenyl sulfones, and the like; amides, for example N,N-dialkyl amides, N,N-alkyl phenyl amides, N-methylpyrrolidinone, N-cyclohexylpyrrolidinone, N,N-diethyltoluamide, and the like; ethers such as alkyl ether derivatives of alcohol, etherdiols, and ethertriols including butylcarbitol, alkyl polyethyleneglycols, and the like; urea, betaine, the thio (sulfur) derivatives of the aforementioned components of, for example thioethyleneglycol, trithioethyleneglycol, and the like; desired penetrants, such as water soluble polymers, pH buffer, biocides, and chelating agents, such as ethylene diamine tetra amine, EDTA and the like. In the inks, the liquid vehicle is generally present in an amount of from about 50 to about 99.5 percent by weight, more specifically, about 55 to about 95 percent by weight, and more specifically, from about 60 to about 90 percent by weight, although the amounts can be outside these ranges.
Examples of ink surfactants include alcohol surfactants, and more specifically, a mixture of secondary alcohols reacted with ethylene oxide, such TERGITOL 15-S(trademark) series surfactants available from Union Carbide, polyethylene oxide, alkylphenoxy-polyethylene oxide such as TRITON X-100(copyright) available from Aldrich Chemical Company, polyethyleneoxide nonylphenyl ether available as IGEPAL(trademark) from Aldrich Chemical Company, or as ANTAROX(copyright) from Rhone Poulenc, Su. The surfactants are utilized in an amount of from about 0.1 to about 5 percent by weight of the ink.
The colorant for the ink compositions of the present invention can be a pigment, or a mixture of one or more, for example from 1 to about 5 pigments, dyes and the like. The colorant can be black, cyan, magenta, yellow, red, blue, green, brown, mixtures thereof, and the like, and is more specifically, Levanyl carbon black obtained from Bayer, IJX-157 carbon black obtained from Cabot Corporation, Mukini JA Black 40M carbon black, Bonjet Black CW-1 and CW-X from Orient Chemical, or Pigment Black 7 Carbon Black Dispersions for ink jet inks obtained from Taisei Chemical Industries. Examples of suitable black pigments include various carbon blacks such as channel black, furnace black, lamp black, and the like. Colored pigments include red, green, blue, brown, magenta, cyan, and yellow particles, and mixtures thereof. Illustrative examples of magenta pigments include 2,9-dimethyl-substituted quinacridone and anthraquinone, identified in the Color Index as CI 60710, CI Solvent Red 19, and the like. Illustrative examples of suitable cyan pigments include copper tetra-4-(octadecyl sulfonamido) phthalocyanine, X-copper phthalocyanine pigment, listed in the color index as CI 74160, CI Pigment Blue, and Anthradanthrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like. Illustrative examples of yellow pigments that can be selected include diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, Cl Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4xe2x80x2-chloro-2,5-dimethoxy aceto-acetanilide, Permanent Yellow FGL, and the like. The preferable pigment dispersions include carbon blacks, such as Hostafine Black (T and TS), Sunsperse 9303, and Levanyl Black A-SF. Of these, Levanyl Black A-SF is preferred in embodiments.
The colorant is present in the ink composition in various effective amounts and generally from about 1 to about 20 percent by weight, more specifically, from about 3 to about 10 percent by weight, more specifically, from about 4 to about 9 percent by weight, and yet more specifically, from about 5 to about 8 percent, although the amount can be outside of these ranges.
Polymeric additives can also be added to the inks to, for example, enhance the viscosity of the ink, which final viscosity is, for example, from about 1, and more specifically, about 15 centipoise to about 100 centipoise at a temperature of, for example, from about 25xc2x0 C. to about 70xc2x0 C., including water soluble polymers such as Gum Arabic, polyacrylate salts, polymethacrylate salts, polyvinyl alcohols, hydroxy propylcellulose, hydroxyethylcellulose, polyvinylpyrrolidinone, polyvinylether, starch, polysaccharides, polyethyleneimines derivatized with polyethylene oxide and polypropylene oxide, such as the DISCOLE(copyright) series available from DKS International, Tokyo, Japan, the JEFFAMINE(copyright) series available from Texaco, Bellaire, Tex., and the like. Polymeric additives may be present in the ink of the present invention in amounts of, for example, from none or zero to about 10 percent by weight, more specifically, from about 0.001 to about 8 percent by weight, and more specifically, from about 0.01 to about 5 percent by weight, although the amounts may be outside these ranges.
Further, optional ink additives that may be present in the ink include biocides such as DOWICIL(copyright) 150, 200, and 75, benzoate salts, sorbate salts, and the like, present in an amount of from 0 to about 10 percent by weight, more specifically, from about 0.001 to about 8 percent by weight, and more specifically, from about 0.01 to about 4 percent by weight, although the amounts may be outside these ranges; penetration control additives such as N-methylpyrrolidinone, sulfoxides, ketones, lactones, esters, alcohols, butyl carbitol, benzyl alcohol, cyclohexylpyrrolidinone, 1,2-hexanediol, and the like, present in an amount of, for example, from 0 to about 50 percent by weight, and preferably from about 5 to about 40 percent by weight, although the amount can be outside these ranges; and pH controlling agents such as acids or, bases, phosphate salts, carboxylates salts, sulfite salts, amine salts, and the like, present in an amount of from 0 to about 1 percent by weight, preferably from about 0.001 to about 1 percent by weight, and more preferably from about 0.01 to about 1 percent by weight, although the amount can be outside these ranges, or the like. Other examples of suitable ink additives include those illustrated in U.S. Pat. Nos. 5,223,026 and 5,207,825, the disclosure of each of which is totally incorporated herein by reference.